Ethers of 2-hydroxy-3.5.x-trichlorodiphenyl



Fatenteci June '10, 1947 ,Gerald 11. Coleman and wesl ycp.

.lvli lan rlli ie h, assignorst T Company, "Mid and 'M e isii-{ERICHLQRO- Nealtrewiae- :An i n J l =45 i342 Serial No. 451,050

wh in R ep esentse m mbe o t e g u ,eeni e ef elke yl alk l e er lkylhal al sexy-e k i .eyel wal g l, a d alls i rad cals- Rep e ntat ve memers Ofjll gro p o 9 mennd 'bave be Premier a el hi h h insfl uiels l lowme in meta n soli -s het en 1 nsolubl in Water an somew t solub e .mmany ersani s l n These compounds are valuable as insecticidal toxicantsand as modifiers for plastic compositions.

In preparing the new compounds '2-hydroxy- 3.5.x-trichlorodiphenyl,isreacted with a suitable etherifying agent in the presence of an alkalimetal hydroxide. Thelreaction is preferably carried out in the=-presenoeof Water or alcohol and at a temperature above 50 C. and below the eeomosit qn tem e a ure o th rea e .IXii t e- "flf iet eriirine a en empeyedi p efab a l fi Qrean e ali .9 a or ani St n er i stant al euimelecula nrener e e e eh eth r isci eae n an pheno ih v be n f undt ivth .siesired t th .eemnound n oo ield- The amount ofalkalimetalhydroxide employed is generally somewhat inexcessof themolecular opor ion phe o pres i th react o mix ure a W en th etheri i ni compl t the rem: tion mixture may be cooled to room temperature,

the ,crude ether product separated by extraction with a suitable solventsuch 1 as --benzene, @Ildjthe extract fractionalsly distilled underreduced pressure. 'The'ether of the 2-hydroxy-3.5.zctrichlorodiphenylmay ;be obtained thereby asasubstantiaIly-=pure--product. -When the crude reaction product is asolid, an alternate purification method ,cOnSistsof fractionallycrystallizing' the reaction -mixture from--a suitable organic solventsuch as petroleum ether;carbon tetrachloride, or alcohol.

A preferred group 9f o0mb .lilfl5 falling Within the scope of thelpresentdnvention are the alkyl ethers or 2 jalkoxy -..3.5.:ctrichlorodiphenyls. These compounds have been found to beparticularlylvhluable.asmodifiers flor pyrtethrum ortrote t.

eun t ihe relenen leit ae s t term flatt red .eqmneei ieee L er hcentre! o i ,m e pests x 5" "i l lllq d p l ih i R111 e mater al in.tner e ret e ue rs ert r red a, m em/ wi hflee ql e s it A., Q ml '9;m9 of emxdmawdkzheml d ss l d in t t aeh l eeti le an the so uti n heat.t 0 9 C- iqm tinle se wa passed th ou t heno se etie a thi tem a u e nt-i t n erese mekl e cle tree ieeiee e v 9 s .Q sa mo e- Th er s .qifleaeen eee eel e d-w roleum ether and recrystallized. After severalrecrystallizations the-re was obtained a 49 per cent yield of2-hydroxy-3.5.x trichloro-riinheny-l ,as ;a white solid r nel ting atlllflilllfiafi G. l'his 16.

of-39per cen atommaszde e .c

benzenerin zthislwa testab ehed bri tle etfsletion of the compound to sorm benzoie a id Throu houtthespeeifieatiqnlandt laimeth htechlorine-atoms are.expressedwas-being in the 3 5- and lmepositions withrespect toel'ihe bend 39mins the two phenyllgroups of :the.= dipheny1radical. The use of w in this capacity shows ,the third chlorine to bein theihydroxylated phenyl group rather than in the unsubstituted thenyl radi al, as i re w th JQ QW whale midwa elie e t1 tee n und vplesete-i ee i'eii te the v s elb tee stw dze limi in -=0==2 qnqla-rproportions of .2+ hydr-oXy -3'.5.w-trichlorodiphenyl and diethylsulfate were reacted togetherinthe presence-Mp3 rno l of sq dium1hydrqxide in lnfljnilliliters of Water. 'The reaction m xtu e wa 1959.1 3; 9 "1 "h and thereafter cooledto obtain asolid product o rea tionwhich .t eetiqeel eryete lie rem petroleum he to the??? stem .e thetlmethe eo r e dream-t5 a tr tlale t i eheay a la twhit er stallme ,eonp lindlme tins a 61- 63 C. This product was somewhat soluble inkerosene, carbon tetrachloride, and 95 per cent ethanol, andsubstantially insoluble in water.

Example 2' Likewise 0.2'molar quantities of z-hydroxy-3.5.:r-trichloro-diphenyl and dimethyl sulfate were reacted together inthe presence of a slight excess of sodium hydroxide dissolved in 100milliliters of water. The crude reaction product was recrystallized fromalcohol to obtain 34.5 grams of the methyl ether of 2-hydroxy-3.5.xtrichloro Example 3 54.7 grams (0.2 mol) of2-hydroxy-3.5.:c-trichlorodiphenyl, 10 grams of sodium hydroxidedissolved in 50 milliliters of water, and 22 grams of normal butylchloride were mixed together and heated to 110-120 C. in a pressurereactor and under autogenous pressure for 6 hours. The crude reactionmixture was then washed with dilute aqueous alkali, extracted withcarbon tetrachloride, and. the extract fractionally distilled. 23.5grams of the normalbutyl ether of 2-hydroxy-3.5.:c-trichloro-diphenylwas thereby obtained as a viscous liquid boiling at 177-1'78 C. at 1.5mm. pressure and having a specific gravity of 1.266 at 25/25 C. Thiscompound was somewhat soluble in 95 per cent ethanol, kerosene, andcarbon tetrachloride, and substantially insoluble in water.

Example 4 54.7 grams (0.2 mol) of 2-hydroxy-3.5.x-trichloro-diphenyl and65 grams of beta-beta-dichloro-diethyl-ether were. mixed together and asolution of 8 grams of sodium hydroxide in 10 milliliters of water addedportionwise thereto over a period of 20 minutes with stirring. Themixture was heated at 90-95 C. for 24 hours and thereafter extractedwith diethyl-ether. The ether extract was fractionally distilled toobtain 10.5 grams of the beta-(Z-chloro-ethoxy) -ethyl ether of2-hydroxy-3.5.x-trichloro-diphenyl boiling at 232-235 C. at 2 mm.pressure and having a melting point of 71-72.5 C. This compound wassomewhat soluble in kerosene, 95 percent ethanol, and carbontetrachloride and substantially insoluble in water.

Example 54.7 grams (0.2 mol) of 2-hydroxy-3.5.m-trichloro-diphenyl wasdissolved in 75 milliliters of 95 per cent ethanol. 20 grams (0.2 mol)of crude allyl chloride, and 8.8 grams of sodium hydroxide dissolved in25 milliliters of water were added alternately and in small portions tothe alcoholic solution over a period of 2-3 hours. The crude reactionproduct was then diluted with water, extracted with benzene and thebenzene extract fractionally distilled to obtain 14 grams of the allylether of 2-hydroxy-3.5.a:-trichloro-dlphenyl as a viscous liquid boilingat 206 209 C. at 4 mm. pressure, and having a specific gravity of 1.386at 25/25 C. This product was somewhat soluble in kerosene, carbontetrachloride, and 95 per cent ethanol and substantially insoluble inwater.

In a similar manner other etherifying agents may be substituted forthoseshown in the examples to obtain such compounds as the isopropyl,tertiaryoctyl, methallyl, n-butenyl, beta- 4 ethoxy-ethyl,beta-n-butoxy-ethyl, beta-propoxypropyl, gamma-(3-chloro-propoxy)-propyl, beta- (2-bromo-ethoxy)-ethyl, cyclohexyl, 4-methylcyclohexyl,benzyl, beta-phenyl-ethyl, and beta- 5 naphthyl-ethyl ethers of2-hydroxy-3.5.r-trichloro-diphenyl.

Representative compounds of the group set forth above have been found'tohave value in insecticidal compositions. In such application they may beemployed in combination with any suitable inert diluent and/or knowninsecticidal toxicant material. A composition comprising 2.5 grams ofthe methyl ether of 2-hydroxy-3.Bm-trichlorodiphenyl, 5 milliliters ofmethyl-ethyl ketone, 50 milligrams of pyrethrum, and suflicient of alight petroleum distillate to give a total volume of 100 milliliters hasbeen found to give a kill against houseflies of 88.4 per cent in 24hours. The pro- .cedure followed in determining the toxicity of thecomposition was substantially that disclosed in Soap 8, No. 4, 1932known as the Feet-Grady method.

We claim:

1. A compound having the formula the formula 01 4a 1|H2n+l wherein n isan integer from 1 to 8, inclusive, ob-

tained by the direct etherification of 2-hydroxy-3.5.:n-trichloro-diphenyl melting at 11'7-118.5 C. 3.2-methoxy-3.5.x-trichloro-diphenyl melting at 77-'79 C. obtained by thereaction of dimethyl sulphate with 2-hydroxy-3.5.a:-trichloro-diphenylmelting at 117-118.5 C. in the presence of aqueous alkali.

4. 2-ethoxy-3.5.x-trichloro-diphenyl melting at 61-63 C. obtained by thereaction of diethyl sulphate with 2-hydroxy-3.5.a:-trichloro-diphenylmelting at 117-118.5 C. in the presence of aqueous alkali.

5. 2-n-butoxy-3.5.r-trichloro-diphenyl boiling at 177-178 C. at 1.5millimeters pressure and having a specific gravity of 1.266 at 25/25 0.,obtained by the reaction of normal-butyl chloride with2-hydroxy-3.5.x-trichloro-diphenyl melting at 117-1l8.5 C. in thepresence of aqueous alkali.

6. A 2-hydrocarbon-oxy-3.5.x-trichloro dipheny1 having the formula,

wherein Z represents an aliphatic hydrocarbon 5 radical, obtained by thedirect etherification of 2-hydroxy-3.5.x-trichloro-diphenyl melting at117-118.5 C.

GERALD H. COLEMAN. WESLEY D. SCHROEDER.

REFERENCES CITED The following references are of record in the file ofthis patent:

Number 6 UNITED STATES PATENTS Name Date Hitch Jan. 3, 1933 StoesserJan. 14, 1936 Clark Mar. 2, 1937 Bass Mar. 1, 1938 Coleman Aug. 29, 1939Coleman Aug. 1, 1939 Coleman Dec. 7, 1943 Certificate of CorrectionPatent No. 2,421,924. June 10, 1947. GERALD H. COLEMAN ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Column 4,lines 69 to 74, inclusive, claim 6, the formula should appear as shownbelow instead of as in the patent and that the said Letters Patentshould be read With this correction therein that the same may conform tothe record of the case in the Patent Oflice.

Signed and sealed this 28th day of October, A. D. 1947.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

